Resinous composition



Patented Dec. 28, 1943 UNITED STATES PATENT OFFICE.

BESINOUS COMPOSITION Gaetano F. DAlelio, Pittsfleld, Mass, asslgnor toGeneral Electric Company, a corporation ,of

New York No Drawing. Application February 17,

' Serial No. 819,516

'15 Claims. (c1. zoo- 4) The present invention relates broadly tousinous compositions and to methods of making the same. It is concernedmore particularly with the production of compositions comprising aresinous reaction product of an alkaline-catalyzedpartial condensationproduct of a phenol and an aliphatic aldehyde with a modified orunmodified acidic esterification product of a polyhydric alcohol and analpha unsaturated alpha beta polyclosed the fact that phenol alcoholsmay be caused to react with flexible alkyd resins having an acid numberbetween 140 and 210 to give satisiactory casting resins. The permanentlyilexible alkyd resins permitted the production of shock-resistantcastings because of the intrinsi flexibility of the alkyd component.

I have discovered that resinous compositions of particular utility ascasting resins, impregnants, etc., can be produced by effecting reactionbetween a partial reaction 'product of a phenol and an'aliphaticaldehyde, specifically formaldeity, designated generally as an with theordinary phenolic resins as bonding agents. The new resins also may beused as laminating adhesives in the production of plywood (a laminatedwood product), in bonding wood veneers to base members of wood, metal,etc., for protectively coating impervious articles such as metals, e.g., iron or copper wire, for coating or coating and impregnatingarticles such as paper, cloth, glass fibers in felted, woven or otherform, etc.

The resinous compositions of this invention are particularly useful ascasting resins. The insoluble and infusible cast resins are capable ofbeing machined and drilled easily, may be produced in clear, transparentand opaque forms and, in general, meet all the practical requirements ofcast resins.

It has been known heretofore that alkyd-modi- In the, copendingapplication of Edmond F.

Fiedler, serial No. 204,620, filed April 2 '7, 1938, now Patent No.2,233,406, and assigned to the same assignee as the present inventiomisdishyde or a polymeric modification of formaldehyde, and an acidices'terification product..of a

polyhydric alcohol with polycarboxylic acid, at

least one such acid being essentially an alpha unsaturated alpha betapolycarboxylic acid. This esterification product (hereafter; forbrevunsaturated alkyd resin") should have pronounced acidity, asevidenced by an acid number of at least 40, but in no case should theacid, partial number be higher than 210. Such definitelyacidesterification products are not, to be confused with 7 neutral orpractically neutral ester bodies having acid numbers of the order of- 0to 20 or 25.

The unsaturatedhalkyd resins, examples 0! which are ethylene glycolvmaleate, diethylene' glycol fumarate', glyceryl itaconate, triethyleneglycol citraconate,-etc., are convertible to the insoluble, infusiblestate through a process of double-bond polymerization. In cured statethey are not permanently flexible even when prepared from a dibasic acidand a dihydric alcohol. Hence it was quitesurprising and unexpected tofind that by co-reacting a phenol-aldehyde partial condensation productwith an acidic unsaturated alkyd resinhaving an acid number not higherthan 210, there could be produced cured, shock-resistant cast resinshaving properties equal to, and in some respect better, than thoseobtained as disclosed and claimed in .the above-identified Fledlerapplications I s In carrying. the present invention into effect a phenolis caused to react, preferably under aqueous conditions, with analiphatic aldehyde..- specifically formaldehyde, in the presence of analkaline catalyst to ing mainly alkylol phenols, specifically methylolphenols (phenol alcohols), or mixtures thereof. This reaction is carriedout at normal or at elevated temperatures, usually under reflux at theboiling temperature of the mass. The choice of the aliphatic aldehydecomponent is dependent largely uponeconomic con form a liquid masscomprissiderations and upon the particular properties desired in thefinished product. I prefer to use .as thealdehydic component (and.always for the product on, of casting resins) formaldehyde or polymericmodifications thereof such as the-poly heatingfor a period sufilcient tocause reaction vtherebetween but insumcient to cause complete separationofthe mass into two-distinct phases,

onmethylenes, e. g.,' paraformaldehyde, trioxy methylene, etc.- For someapplicationsof the finished resin I may use other aliphatic aldehydes,for instance acroleinyacetaldehyde, propionaldehyde, butyraldehyde,"crotonaidehyde,

etc mixtures thereof or mixtures of formaldehyde (or compoundsengendering formaldehyde) with such aliphat c aldehydes In general, "thelonger the chain of the aliphatic aldehyde, the" Y softer is the finalproduct.

Any phenol having aldehyde-reactive positions in the ring may beemployed. The choice of. the

' aldehyde-reactable phenolic body'also' .depends upon economicconsiderations and the-particular properties desired in the end-product.Thus, for

. the production or oil-soluble resins, I may use that is, insuificientto form a distinct oily layer of 'the resinous condensation product.Thereafter an acidic unsaturated alkyd resin having an 'acid number nothigher than 210 is incorporated into the liquid, resinous phenolaliphatic aldehyde partial condensation product and the mixed componentsare caused to react further, preferably at a temperature notexceedingsubstantially 110. C.,'thereby toform a potentially reactive resinouscomposition capable of convertingunder heat to an insoluble, infusiblestate. I The acidic unsaturated alkyd resin is separately prepared, thatis, preformed, in accordance with technique now well known to thoseskilled in the alkyd resin art. Any polyhydric alcohol orthoorpara-substituted phenols such, for example, as disclosed in mycopending' application Serial No. 319,515, filedconcurrentlyherewith andassigned to the same' assignee as the present invention. For'theproduction of casting resins I prefer to use a V mula phenol having thegraphic forcontaining at least two esterifiable aliphatic hydroxylgroups, or mixtures of such alcohols, may be used in preparing theunsaturated alkyd resin. Examples of such polyhydric alcohols areethylene glycol, di-, triand tetraethylene. glycols, propylene glycol,trimethylene glycol, thiodiglycol, glycerine, pentaerythritol, etc. Anyalpha unsaturated alpha beta polycarboxylic acid, or mixtures of suchacids, may be reacted with the polyhydric alcohol or alcohols to formthe unsaturated al- I kyd resin. -.Examples of such polycarboxylic acidswhere R isv a memberofthe group consisting of hydrogen, alkyl radicals(e. g methyl, ethyl. propyl, butyl, etc), 'aryl radicals (e. g., phenyl,

oresyl, etc.) and-alkoxi radicals (e. -.-m XY. ethoxy, etc.).

The ratio of aliphatic'aldehyde to phenol may be varied over a widerange, but preferably is within the ratio of 1 mol phenol. to i to 4 0r5 mols aliphatic aldehyde. For producing castingresins I have obtainedbest results by using 1 mol phenol to approximately 1.5, to 3'mols form-"aldehyde. 15y varying the-ratio of phenol to formaldehyde, the rate ofcure and the strength .stantially 100. C.

of the final product may be varied.

The alkaline catalyst employed advantageously is one which has'nodarkening eflect upon the resin. Hydroxides of the alkaline-earth metals(calcium, strontium and barium) and hydroxides,

metals. (lithium, sodium, potassium, rubidium and caesium) are examplesof suitable catalysts. The 7 amount of catalystmay be considerablyvaried, but generally is about 0.5 to 5 per cent by weight of thephenolic body. The nearer the reaction temperature approaches 100* (2.,the less catalyst is required At reaction temperatures. of approximately60- to 90 C. an amount of catalyst ranging from about 1 .to 3.5 per centby weight .of the phenol usually is effective. The catalystconcentration generally will be somewhat lower,

other conditions being the same, when hydroxides .of the alkali metalsareused, as compared with the corresponding alkali-metal salts such ascarbonates, cyanides and'borates.

In producing casting resins the initial reaction temperature between thephenol and formaldehydepreferably is-not' permitted toexceed'subrated-alkyd-modified phenolic-resin may be ob'- jectionablydarkened. a

The phenol and aliphatic aldehyde are intiare maleic, monohalomaleic,fumaric, monohalofumaric, citraconic, mesaconic,' acetylejrl'e dicaranitrogen atmosphere, until anacidic unsaturated alkyd resin havingalcoholic 'hydroxyl "groups and an acid number not higher than 210is-obtained. Such a resingenerally will be pro- 'duced when thecomponents have been reacted until from about 55 to 93 per cent of thetheoretical water of esterification has been collected. Acidicunsaturated alkyd resins having an acid number higher than 210 shouldnot be used, since a largeexcess of unreacted unsaturated alkyd resincomponents (indicated by an acid number carbonates, cyanides and boratesof the alkali I above 210) has a detrimental efiect upon the curedproduct. I V

'In some. case s,.instead of using an unmodified unsaturated alkyd resinI may mean acidic unsaturated-alkyd resin which has been internallymodified by replacing a part, say up to about 75 mol per cent ofthe'alpha unsaturated alpha beta polycarboxylic acid with anon-ethylenic polycarboxylic acid, e. g., a saturated aliphaticpolycarboxylic acid such as succinic, adipic, giutaric, pimelic,sebacic, azelaic, suberic, tricarbaliylic, tartaric, citric, etc.,cyclic polycarboxylic Otherwise the cured, unsatuacids, morespecifically the saturated cycloali phatic polycarboxylic acids suchasthe cyclo propane dicarboxyiic acids, the cyclohexane dicarboxylicacids, the alkyl cycloalkane polycarboxylic acids, etc., and thearomatic polycarboxylic acids, e. g., phthalic, benzoyl phthalic,terephthalic, benzophenone-2,4' dicarboxylic acids, etc. or withanhydrides' of such, acids if available. The thus modified acidicunsaturated alkyd resin, thepolycarboxylic acid component of whichcontains at least 25 mol per cent alpha unsaturated alpha betapolycarboxylic acid, like! wise should have an acid number not higherthan.

mately associated, for example by mixing and 76210.

The term "unsaturated alkyd resin" at generally'herein and in theappended claims is intended to include within its meaning bothunmodiiied esteriilcation products of. a polyhydric alcohol with analpha unsaturated alpha beta polycarboxylic acid and esterificationproducts of the said'components which have been modifled with anon-ethylenic polycarboxylic acid such as above described. The terms"polycarboxylic acid and dicarboxylic acid as used generally herein andin the appended claims are used intended to include within their meaningthe known anhydrides of the acids.

As is well known, when a phenol and an aliphatic aldehyde are caused toreact under alkaline conditions a phenol alcohol forms first.

As the reaction proceeds, a condensation product that at first causesthe mass to become milky 0r opalescent is produced. If the'reaction isa1- lowed to proceed furthers. separation of the mass into an aqueouslayer and a thick, syrupy,'

oily resinous layer takes place. In carrying the presentinvention intoefl'ect a soluble, acidic unsaturated alkyd resin oi' not higher than210 acid number may be incorporated with the phenolic reaction productwhen the latter is in the 3 is employed a a catalyst for the.phenol-aldehyde reaction, it is sometimes advantageous to use lessacidic unsaturated alkyd resin than would be required to neutralizecompletely the alkalinity of the phenolic reaction product. In suchcases neutralization is completed by adding asuitable amount or anorganic carboxylic acid such as acetic, propionic, .oxalic, malonic,succinic, adipic, acrylic, methacrylic, polymethacrylic, maleic,iumaric, citraconic, tartaric, citric, lactic, hydroxy malonic, etc. Inthis way the amount of acidic unsaturated alkyd resin required forneutralization may be materially reduced.

- 'For casting resin application, but not necess'arily for other uses ofthe resin, it is important that the temperature of dehydrating theunsatuform of a clear solution comprising mainly a mix-' mixedcomponents then are reacted further. The

mixture may be heated for a short time prior to dehydration orimmediately may be dehydrated.

In the latter ,case the phenol-aldehyde partial condensation product andthe unsaturated alkyd resinco-react simultaneously with the dehydrationof the resinous mass.

The amount of unsaturated alkyd resin incorporated into thephenol-aldehyde initial reaction product may be varied over a widerange. The

optimum proportion of unsaturated alkyd resin to phenolic resin dependsupon such influencing factors as, for example, the particular startingcomponents and proportions thereof employed in the production of theunsaturated alkyd resin and the phenolic resin, the particularreactiontime and temperatures and the particular properties desired in theend-product. However,'generally speaking the unsaturated alkyd resincomponent will be not more than '75 per cent by weight of the dehydratedor cured resinous mass and, for casting resin-applieations, will be notmore than per cent by weight thereof. In most cases casting resinsproduced in accordance with this invention are constituted ofunsaturated alkyd resin ln an amount corresponding to from 5 to 45 percent by weight oi the dehydrated or' cured resinous mass. Particularlygood results have been obtained with, by weight, from 5 to 30 per centunsaturated alkyd resin to '95 to '70 per cent phenolic resin based onthe dehydrated mass. In general, the harder it is desired that the curedresin should he, the less the amount of unsaturated alkyd resin used.

When a strong base in relatively large amount rated alkyd-phenolic resinintercondensation product does not exceed substantially 110' C.

Preferably the mass is so dehydrated under re- .duced pressure that themaximum temperature attained is not higher than or C. It a temperatureof 110 is attained during dehydration, the cured resin may form starcracks in the cast object. Such cracks are objectionable i'rom' thestandpoint both of appearance and maximum strength of the casting. Ifthe maximum temperature of dehydration is, say C, the cured product willbe darker than if the maximum is,

for example, 70 or 80 C.

During theprocess of curing the cast resins of this invention: in moldsthe resin temperature should not exceed substantially C. The higher thecure temperature, the more rapid the cure but the darker is the curedproduct. Best results are obtained by curing at a temperaturewhich doesnot exceed substantially 100 C. and

which preferably is of the order oi' '75 to 90 C.

Lower curing temperatures, for example iii)v to 709 C. may be used, butthe curing. process then proceeds much more slowly.

When the resinous compositions of this invention are used in laminatingand adhesive ap- 'plications, the resin may be cured in situ at muchconverted to the insoluble, iniusible stateinabout higher temperatures,for example at temperatures of the order of or- C.- At such temperaturesthe soluble, fusible resinous niass is 30 to 60 minutes.

When it is desired to color the resin a suitable dye or pigment isadded, preferably shortly before or immediately after the completion ofthe dehydration step and while the resin is still in the reactionvessel.

'In order that those skilled in the art better may understand how thepresent invention may be carried into eflect, the following examplesthereof are given by way of illustration:

EXAMPLE 1 Parts by weight 90.0

Phenol Aqueous solution of formaldehyde (approximately 3'1.1% HCHO)161.0 Sodium hydroxide in '5 parts water 0.9 Acidic ethylene glycolmaleate (acid number below 210) 40.0

40 parts of acidic ethylene glycol maleate ob- Phenol Sodium hydroxidein 10 parts water";

alcohols.

' Bameiormula as in Example'z with tained by reacting 62 as. (-1" mol)ethylene glycol and 98 parts (1 mol) maleic anhydride in;

a nitrogen atmosphere for ,5 hour at 180 to 190 C., during which time70' per cent of the calculated water of esterification was collected.After thoroughly mixing the ethylene glycol maleate with the phenolicresin, the mass was dehydrated under. a vacuum of 26.5 inches ofmercury. During dehydration the resinous mass reached a maximumtemperature of 92 C. The

' hot resin was poured into m ids and cured therein at approldmately 8 5C. for '72 hours. Thecured articleswere hard, tough and exceptional- 1ylight-colored, having the visual appearance of opalescent glass.

EXAMPLE'Z Preparation of phenolic resin I Parts by weight 94 Aqueoussolution of formaldehyde (approximately 37.1% HCHO) 161 1 The abovecomponents were mixed and heat- The acidic ethylene glycol itaconate wasprepared by 47 parts (1.5 mole) ethylene glycol with 65 parts (1 mol)itaconic acid in a nitrogen atmosphere for ,5 hour at 185 to 195' C.,during which time 83 per cent of the theoretical water of esteriflcationwas collected.

' The above components were mixed and the mixed under reflux at boilingtemperature (approximately 94 to 98 C.) for minutes. The resultingliquid 'mass was a clear, homogeneous solution comprising mainly amixtureof phenol J lfarts' byweight Phenol-formaldehyde partialcondensation product prepared as described above.. 25.0 a

Acidic ethylene glycol itaconate (acid number below 210) s 2.3

The acidic ethylene glycol itaconate was'produced by reacting 62 arts(1.0 mol) ethylene glycol with 130 parts (1 mo) itaconic acid in anitrogen atmosphere or 1% hours at approximately 180 to 195 C.' duringwhich time 93 r cent of the calculated water of esteriilcation was colected.

The acidic ethylene glycol itaconate was thoroughlymixed with thephenolic resin, yielding a mass which was slightly acid to litmus. 'Thismass was dehydrated under 'a vacuum 01' 4 mm.

mercury, the temperature being 30' C. at the end 1 of the dehydrationperiod. A clear, viscous resin was obtained. This resin was poured intoa mold and cured therein at approximately 100 C. for 48 hours, yieldinga hard, tough. amber-colored opaq e casting.

' Exmnz 3 Same formula as in Example 2 with the excep tion that 12parts, instead of 2.3 parts, 0! ethylene glycol itaconate were mixed andcaused to react with the phenolic resin. The'mixed components 70' C.during dehydration. The dehydrated mass was a clear, pink-colored resinwhich was cast and cured at 100 C. for 48 hours, yielding a hard, almosttransparent, amber-colored casting.

nternal 4 7 a v V the exception that 5 parts ethylene glycol itaconatewere used. The mixture ciphenolic resin and acidic ethyleneg'lycolitaconate was dehydrated 'imder a vacuum of 2 mm. jmercury, thetemperature being 40 C. at the end ofthe dehydration period.

The resulting-clear, viscous resin poured into a mold and cured thereinat 100 'C. for 48 hours;

The cured resin was hard, opaque and 0! an amber-color.

' itaconic acid -in ture dehydrated under a vacuum or 30 mm. mercury.During :dehydration the resinous mass reached a maximum temperature of105 C. A viscous resin oi. water-white clarity was obtained. A sample ofthis resin cured in a mold after 6 weeks heating at about 60 C. to arubbery, white, opaque state. Another sample formed a hard,

white, opaque resin after heating for 10 days at 1 90 C. in a mold.

Exnrrts 6 V v Parts by weight Phenol-formaldehyde partial condensationproduct prepared as described under Example 2' I Acidic glycerylitaconate (acid number be- I low 210) The acidic glyceryl itaconate wasdre ared by reacting 62 parts (0.67 mol) glycerine with 13 parts (1 mol)a nitrogen atmosphere for 5 hour at 180 C., during which time 55 waterof esteriiication was co lected.

The above components were mixed and the mixture dehydrated under avacuum of 6 mm. mercury, the-temperature being 40 C. at the end or thedehydration period. The resulting clear, viswere dehydrated under-avacuum or 4 mm. mercm. the temperature reaching a mammal ice cous resinwas poured into a mold and cured therein at 90 C. for hours. The curedresin was hard, opaque and of an amber color.

Exams; '7

Phenol-formaldehyde partial condensation product prepared as describedunder Example 9 v 25 Acidic glycerylitaconate (acid number below 210)prepared as described under Exam- Pie 6 p 5 The mixed components weredehydrated under a vacuum 015 mm. mercury, the temperature bemg 60' C.at the end oi! the dehydration period.

The resulting clear. viscous resin was cured in a J mold at C. for 60hours, yielding a hard,

translucent, amber-colored resin. i

Exams: 8

Parts by weight Phenol-formaldehyde partial condensation productprepared as described under Exmp e 2 f Acidic glyceryl itaconate (acidnumber below 210) prepared as described under Exam- Die 6 Themixedcomponents were dehydrated under a vacuum of 4 mm. mercury, thetemperature being 60 C. at the end 01' the dehydration period.

Aclear, viscous resin was obtained. The hot resin -was poured intoa moldandcured therein at .90 C. for 60 hours, yielding a hard; clear cast ercent of the calculated Parts by weight Emmi-s 9 Preparation of phenolicresin Parts by weight Phenol 47.0

' Aqueous solution of formaldehyde (approximately 37.1% HCHO) --a 88.0Sodium hydroxide in parts water 0.48

. parts glycerine (1.2 mols) and 65 parts itaconic acid (1 mol) in anitrogen atmosphere first at 125 to 160 C. for 35 minutes and then atabout 190 to 195 C. for about 20 minutes. The mixed components wereheated under reflux at the boiling temperature of the mass for 40minutes and then dehydrated under 26 to 28- inches vacuum until 40 partswater of reaction had been removed. The dehydrated resin was heated in amold for 6 days at 70 C., yielding a slightly rubbery, tough mass.

Instead of effecting reaction between the phenol and aliphatic aldehydeas above described, that is, under reflux at the boiling temperature ofthe mass, the components may be reacted at room temperature (20 to C.)or first at 'temperatures of the order of 50 to 60 0., followed byfurther reaction at room temperature.- Reaction temperatures of, say, 70to 85 C. also may be employed, in which cas the reaction time generalLvwill be between about one and two hours.

a The longer the reaction time at such temperature, the more viscous theresin becomes during subsequent dehydration. The casting of too viscousa resin has a tendency to yield .a cured resin containing bubbles ofentrapped gas. Higher or longer reaction temperatures require shorter orlonger reaction periods to obtain dehydrated, potentially reactive,resinous materials of approximately the same viscosity.

To obtain light-colored products, materials of a high degree of purity,should be used. The phenol should be a specially distilled materialsubstantially'free from bodies capable of imparting color to the curedresin. The catalyst should meet the specifications of the United StatesPharmacopoeia for purity, or be of an equivalent grade. The purestavailable aliphatic aldehyde should be employed. The unsaturatedalkydresln should be almost water-white.

coils which, after curing, are the equivalent oi a molded coil. With orwithout solvents they may be used as impregnants. for many porousbodies, such as cork, pottery, felts or fabricated bodies withinterstices, netted fibers, interwoven fibrous materials, concrete,synthetic boards, etc.

Bubble-free cast resins of uniform characteristics from batch to batchcan be produced in accordance, with this invention. The rate of curin iscomparable with, and in many cases better than. that of casting resinsproduced by other methods and of diflerent composition. The curedproducts are mechanically strong and of varying degrees of toughness,depending upon such factors as above set forth. The strength of thecured resin,.as measured by breaking a -inch diameter by 5-inches longcylinder on a Charpy testing machine, ranges from about 0.7 footpoundtoabove the measuring capacity of the machine,

' which is 2 foot pounds. The cured cast resins of this invention arewater-resistant, oil-insoluble and extremely resistant to ultra-violetlight.

The liquid casting resins, with or without modifying agents, may be castin any desired shape and molded under heat orunder heat and pressure.They can be turned easily on a lathe, or drilled, without chipping orcracking, and may be employed to make a wide variety of useful articles.

receiving sets, radio cabinets, vases and umbrella handles.

Specific examples of fillers and other modifying agents which may beincorporated into the resinous compositions of this invention prior to,

use are lignin, partially hydrolyzed wood, wood fiour, alpha cellulose'in flock form, sand, clays, asbestos, mica, Paper, cloth, cellulosederivatives such, as regenerated cellulose, cellulose esters,

.such as the oxides, the phthalates, etc., may also be incorporatedintothe compositions.

In my copending application Serial No. 319,515, filed concurrentlyherewith and assigned to the same assignee as the present invention, 1have The properties of the cured resins can be varied considerably byvarying the starting components and the proportions thereof. Forexample, the toughness and flexibility of the heat-hardened resin can bevaried by using difierent polyhydric alcohol esters of alpha unsaturatedalpha beta,

polycarboxylic acids. By using the longer. chained polyhydric alcohols,e. 8., diethylene glycol, triethylene glycol, etc., in preparing theacidic unsaturated alkyd resin component, the final product tends --tobe more flexible. Transparent as well as translucent 0r opaque effectsmay be produced byvarying the formula and extent of dehydration.

The dehydrated resins before curing are sufilciently liquid that theymay be poured without dimculty. Hence they may be used in coating,impregnating and similar applications without added solvent. They may beemployed, for exdisclosed and specificallyclaimed oil-soluble resinouscompositions produced by reacting an acidic unsaturated alkyd resinhaving an acid number not higher than 210 with an alkalinecatalyzedpartial condensation product of an allphatic aldehyde with an orthoorparasubstituted phenol containing at least four carbon --densationproduct of ingredients consisting of a ample, to impregnatepaper-insulatedlayerwound the said condensation product and obtained byExamples of such articles are rods, sheets, tubes, clock cases, doorknobs, telephone clyhydric alcohol and polycarbcxylic acid, at i leastone such acid being essentially an alpha unsaturated alpha betapclycarboxylic acid forming at least 25 mol per cent of 'thepolycarboxylic acid, and (2) a liquid alkaline-catalyzed partialcondensation product of ingredients consisting of 7 formaldehyde andphenol obtained by reacting 2o 7 said ingredients fora period suificientto cause reaction'therebetweenbut insuflicient to cause completeseparation of the reaction mass into two distinct phases, said alkydresin having an acid number of at least 40 and not higher t an 210,being compatible with the said phenolformaldehyde-partial condensationproduct and constituting from 5 to 50 per cent by weight of the saiddehydrated reaction product.

3. A composition as in-claim 1 wherein the unsaturated alkyd resin is anacidic polyhydric alcohol itaconate having an acid number of at least 40and not higher-than 210.

4. A composition as in claim 1 wherein the un- 1 saturated alkyd resinis an acidic polyhydric alcohol maleate having an-acid number-oi atleast 40 and not higher than 210.

5. A composition as in claim 1 wherein the unsaturated alkyd resin is anacidic poly ric alcohol fumarate having an acid number of 'at least 40and not higher than 210.

.6. A heat-curable resinous product of partial reaction of ingredientsconsistingoi (1) a liquid alkaline-catalyzed partial condensationproductof ingredients consisting of phenol and formaldehyde obtained byreacting said ingredients for a period suilicient to cause reactiontherebetween but insufiicient to cause complete separation of thereaction mass into two distinct phases A and (2) a preformed acidicunsaturated alkyd resin compatible with the said condensation productand obtained by incomplete reaction 01 ingredients' consisting ofpolyhydric alcohol and alpha unsaturated alpha beta polycarboxylic acid,said alkyd resin having an acid number of at least 40 and not higherthan 210 and con-V fstituting from to 75 per cent by weight or the saidresinou product in cured state.

' 'L-A product comprising the cured resinous composition of claim 6.

8.'A composition comprising the dehydrated resinous reaction product oringredients consist-- ing of (1) a phenol alcohol and (2) a preformedacidic unsaturated alkyd resin compatible with the phenol alcohol or (1)and obtained by incomplete reaction oi ingredient consisting ofpolyhydric alcohol and polycarboxylic acid, at least one such acid beingessentially an alpha unsaturated alpha beta polycarboxylic acid form--ing at least mol per cent of. the polycarboxylic acid, said alkyd resinhaving anacid number or at least and not higher than'21o and constituting from 5 to '75 percent by weightoi the said dehydrated resinousreaction product j 9. A dehydrated resinousreaction product 0!ingredients consisting or (1). a preformed acidic "unsaturated alkydresin obtained by incomplete reaction of ingredients consisting ofpolyhydric alcohol and an alpha unsaturated alpha beta 1 polycarboxylicacid and (2) a liquid alkalinecatalyzed partial condensation product ofingredients consistingof l mol of a phenol and from 1 to 5 mols of analiphatic aldehyde obtained by reacting said ingredients for a periodsufiicient to cause reaction therebetween but insufficient to causecomplete separation'of the reaction mass into two distinct phases,said-alkyd resin being compatible with the condensation product of (2),having an acid number or at ea t 0 a d ot higher than 210 andconstituting from 5 to per cent by weight of the said dehydrated reac- Ytion product.

10. A casting resin adapted tobe cured within the temperature range of'60 to 110-C., said resin being the clear, viscous, resinous partialreaction product of ingredients-'consisting-oi (l) a preformed acidicunsaturated alkyd resin obtained by incomplete reaction of ingredientsconsisting of polyhydric alcohol and polycarboxylic acid, at least onesuch acid being essentially an ..alpha unsaturated alpha betapolyo'arboxylic acid forming at least 25 mol per cent of thepolycarboxylic acid, and (2) a liquid alkaline-catalyzed partialcondensation productot ingredients 'consisting'of approximately 1.5 to 3mols rormaldehyde with 1 mol of phenol obtained by re-- acting saidingredients for a period suiiicient to cause reaction therebetween butinsuflicient to cause complete separation oi the reaction mass into twodistinct phases, said alkyd resinihaving an acid number of at least 40and not higher than 210, being compatible with the saidphenoliormaldehyde partial condensation product, and constituting from 5to 30 per cent by weight of the said casting resin in cured state.

-11. The cured casting resin of claim 10,7said resin being machinableand drillable without chipping or cracking, and being furthercharacterized by its freedom from bubbles,-oil-insolubility andresistance to water and ultra-violet light;

' 12. A composition comprisingthe dehydrated Y resin obtained byreaction during dehydration of a mixture of ingredients consisting of(1) a liquid partial condensation product of ingredients consisting .ofphenol and an aldehyde comprising mainly phenol alcohols and (2) a.preformed acidic unsaturated alkyd resin obtained by in-.,

complete reaction of ingredients consisting'oi a dihydric alcohol and analpha unsaturated alpha beta polycarboxylicacid, said alkyd resin havingan acid number or at least 40 and not higher than 210, being compatiblewith the said liquid mass or (i) and constituting Irom 5 to 30 per centby weight or the said dehydrated resin.

,13. A dehydrated resinous product or reaction of ingredients consistingof (1) a liquid alkalinecatalyzed partial condensation product ofingredients consisting. of a phenol andan aliphatic aldehyde obtainedbyreacting said ingredients in a period sufllcient to cause reactiontherebe! tween but insuiilcient to cause complete separation of thereaction mass into two distinct phases,

and (2) a preformed acidic ur'isaturated alkyd resin obtained byincomplete reaction or ingredientsconsisting or polyhydric alcohol,alpha unsaturated alpha beta polycarboxylic acid up to about 75, mol percent of the said unsaturated polycarboxylic acid of a polycarboxylic "1acid selected from the class consisting 01 Bit:

urated aliphatic polycarboxylic acids and aromatic polycarboxylic acids,said alkyd resin having an acid number 01' at least 40 and not higherthan 210, being compatible with the said partial condensation product of(1) and constituting from 5 to 75 per cent by weight of the said,dehydrated reaction. product.

14. The method which comprises incorporating into a liquid massconsisting oi the partial condensation product oi ingredients consistingoi phenol and an aldehyde and comprising mainly phenol alcohols apreformed acidic unsaturated alkyd resin compatible with said liquidmass and obtained by incomplete reaction of ingredients consisting oipolyhydric alcohol and polycarboxylic acid. at least one such acid beingessentially an alpha unsaturated alpha beta polycarboxylic acld'iormingat least mol per cent oi the polycarboxylic acid, and; causing the saidalkyd resin to react with the said liquid mat a temperature notexceeding substantially 110 C. to form a heat-curable resinouscomposition,

said alkyd resin having an acid number of at least and not higher than210 and the amount thereof which is incorporated into the said liquidmass being 'such that it constitutes from 5 to per cent by weight of theheat-cured resinous composition. 15. The method which compriseseffecting reaction at a temperature not exceeding substantially C.between ingredients consisting of an aqueous solution of fromapproximately 1.5 to 3 mols formaldehyde and 1 mol of phenol,

said reaction being carried out in the presence of an alkaline catalystfor a period sufllcient to form a liquid phenol-formaldehyde partialcondensation product but insufficient to cause complete separation ofthe reaction mass into two distinct phases, incorporating into the saidliquid product a preformed acidic unsaturated alkyd resin compatibletherewith and obtained by incomplete re--, action of ingredientsconsisting of polyhydric alcohol and polycarboxylic acid, at least onesuch acid being essentially alpha unsaturated alpha beta polycarboxylicacid forming at least 25 mol per cent of the polycarboxylic acid, anddehydrating the resulting mass at a temperature not exceedingsubstantially 0. simultaneously with effecting co-reaction between thesaid alkyd

